CN105384656B - A kind of method of cyclohexanone oximate - Google Patents
A kind of method of cyclohexanone oximate Download PDFInfo
- Publication number
- CN105384656B CN105384656B CN201510698820.7A CN201510698820A CN105384656B CN 105384656 B CN105384656 B CN 105384656B CN 201510698820 A CN201510698820 A CN 201510698820A CN 105384656 B CN105384656 B CN 105384656B
- Authority
- CN
- China
- Prior art keywords
- cyclohexanone
- oximate
- solution
- cyclohexanone oxime
- oximation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
- C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of cyclohexanone oximation process, in the production process for being particularly suitable for use in flue gas desulfurization by-product cyclohexanone oxime, the present invention is absorbent using ammonia or ammoniacal liquor, absorb the sulfur dioxide in flue gas, prepare ammonium bisulfite, as raw material and hexamethylene reactive ketone, adverse current oximate obtains cyclohexanone oxime.The present invention improves the diffusion of reaction system, reduces the consumption of cyclohexanone by improving the concentration of HAS and the addition of organic solvent；Simultaneously as cyclohexanone oxime, cyclohexanone total content can be reduced to below 0.30wt% in organic solvent extraction, the inorganic phase of the invention for leaving cyclohexanone oxime synthesis system, the yield of cyclohexanone oximation reaction is improved.
Description
Technical field
The invention belongs to chemical technology field, it is related to a kind of method of cyclohexanone oximate, and in particular to a kind of ammonia flue gas
Desulfurizing byproduct HAS and the method for cyclohexanone oximate.
Background technology
Cyclohexanone oxime is the critical materials of caprolactam, and caprolactam is production nylon 6 fiber (cotton synthetic fibre) and the work of nylon 6
The important monomer of engineering plastics, is widely used in the fields such as automobile, ship, medical article, commodity, electronics and electronic component.Nothing
By being widely used cyclohexanone oxamidinating technology, or HPO technologies at present, the intermediate products of production caprolactam are all hexamethylenes
Ketoxime, and key problem in technology is also the production of cyclohexanone oxime.Caprolactam is translated into after the rearranged reaction of cyclohexanone oxime.Mesh
Before, the oximes method of hydrogen peroxide and HPO methods are mainly applied in cyclohexanone oxime production.In recent years, with caprolactam demand and production capacity
Continuous expansion, its production scale expands rapidly, and cyclohexanone oxime has the huge market space.
The production method for producing caprolactam using cyclohexanone oxime belongs to traditional cyclohexanone-hydroxylamine assay.Such method is
The main method of caprolactam is produced by raw material of cyclohexanone.Wherein the production process route of azanol mainly has three kinds again, respectively
It is HSO methods, HPO methods, NO methods.HSO methods are HAS method.HAS method is with ammonia and sulfur dioxide reaction production sulfuric acid hydroxyl
Amine, the method that the HAS then obtained generates cyclohexanone oxime with hexamethylene reactive ketone.The method mature technology, investment
Small, simple to operate, security is good, but has distinct disadvantage, its raw material NH3And SO2Consumption is big, make the technology compare HPO methods,
NO methods are more less economical.After method using ammonia type flue gas desulfurizing by-product production cyclohexanone oxime, the sulphur in flue gas make use of to provide
Nitrogen resource in source and desulfurization solvent, has a extensive future.
The process that HAS solution reacts generation cyclohexanone oxime under certain condition with cyclohexanone is referred to as cyclohexanone oximate,
Course of reaction produces sulfuric acid, commonly uses in ammonia and generation ammonium sulfate.
Key reaction formula is as follows：
1/2H2SO4+NH4OH→1/2(NH4)2SO4+H2O
Cyclohexanone oximation process has interval oximate, continuous oximate and adverse current oximate etc., and interruption oximate is in Large Scale Industrial Process
In be eliminated.During continuous oximate, to ensure the conversion of cyclohexanone, azanol consumption typically requires more than the 3-8% of theoretical amount, excessive
Azanol lost with the ammonium sulfate liquor of oximation reaction.Even under such charge ratio, cyclohexanone can not still turn completely
Cyclohexanone is turned in cyclohexanone oxime, products obtained therefrom cyclohexanone oxime still more than 0.1%.This not only adds the consumption of cyclohexanone,
And the quality of influence final products caprolactam.Leave cyclohexanone oxime, cyclohexanone in the inorganic phase of cyclohexanone oxime synthesis system
Total content is high, usually above 0.3wt%, causes cyclohexanone oximate yield low.Cyclohexanone oximation reaction generation cyclohexanone oxime because
Viscosity is larger, and difficulty is spread in reaction system, causes the problem of oximation reaction speed is low.
In the case of using ammonia type flue gas desulfurizing by-product cyclohexanone oxime, also in the presence of some specific questions.Generally, factory discharges
Flue gas in SO2Content is low, often less than 5000ppm, as SO in flue gas2When concentration is low, easily there is ammonia type flue gas desulfurizing by-product
HAS solution concentration is low, causes sulfate water content in oximate process inorganic phase high, and crystallization process water removal heat dissipation is big and has
Machine solution loss.
The content of the invention
Goal of the invention：It is an object of the invention to provide a kind of method of cyclohexanone oximate, flue gas desulfurization byproduct sulphur is utilized
Sour azanol produces cyclohexanone oxime in high yield.
In technical scheme provided by the present invention, the production process for being particularly suitable for use in flue gas desulfurization by-product cyclohexanone oxime, profit
It is the sulfur dioxide in absorbent absorption flue gas with ammonia or ammoniacal liquor, prepares ammonium bisulfite, remove solid impurity therein
Afterwards, reacted with nitrite, sulfur dioxide, HAS solution is prepared, using this HAS solution as raw material and hexamethylene
Reactive ketone, obtains cyclohexanone oxime.
Specifically, being that hydroxylammonium sulfate solution is improved into concentration, oxime is then carried out using the method for adverse current oximate with cyclohexanone
Change reaction；The method for improving concentration is to remove water the vacuum flashing of high-temperature sulfuric acid hydroxylamine solution in hydrolysis latter stage, or is added
Hot hydroxylammonium sulfate solution evaporation water removal.
In the adverse current oximation reaction, the mol ratio of cyclohexanone and HAS is 1:1-1:1.06.
HAS solution concentration is 0.8-3.1mol/L, preferably 2.4-3.0mol/L. in said process
In said process, the adverse current oximate is two sections of adverse current oximates or multistage counter current oximate.When using two sections of adverse current oximes
During change, wherein first paragraph material cyclohexanone：HAS mol ratio is 1.4:1, second segment material cyclohexanone：HAS mole
Than for 1:4.Above-mentioned two sections of adverse current oximates, every section is made up of one or two reactor.
Further, organic solvent, the organic solvent are added (in first paragraph oximate system) during oximation reaction
Solubility at 20 DEG C in water is less than 0.1%wt.The organic solvent is benzene,toluene,xylene, methyl cyclopentane, ring
One kind in hexane, or a variety of mixtures.
More specifically, oximation process provided by the present invention, be respectively：One, two section of four Anticountra flow oximate, two, two section two
Anticountra flow oximate.The reactor can be tank reactor, tower reactor, tubular reactor with stirring etc..
Oximation process one：Two section of four Anticountra flow oximate, (by taking tank reactor as an example) as shown in Figure 2.
The latter stage of HAS, i.e. hydrolysis latter stage are prepared, the vacuum flashing of high-temperature sulfuric acid hydroxylamine solution concentration is removed water,
It can also be the solution concentration evaporation water removal of heating HAS, typically require that HAS solution concentration is more than 0.8mol/L.
Ammonium sulfate by cyclohexanone and containing HAS is added in the first oximation reaction device, and is passed through simultaneously few
Ammonia is measured, makes solution overflow to the second oximation reaction device, continues logical ammonia, temperature maintains 55-65 DEG C, and pH value is maintained at 4 or so.Instead
Answer liquid to flow to ammonium sulfate extraction separator by the second oximation reaction bottom, organic solvent is added into extraction separator.Separator
Upper strata is cyclohexanone, cyclohexanone oxime liquid and organic solvent, removes cyclohexanone oxime line pump groove；Lower floor is ammonium sulfate liquid, removes ammonium sulfate
Crystallization apparatus.
Cyclohexanone, the cyclohexanone oxime liquid sent by the HAS after concentrate and by cyclohexanone oxime line pump groove are added to
Three oximate reactors, while logical ammonia, control reacting liquid pH value is 2 or so, and temperature is at 60-70 DEG C.Reaction solution is anti-by the 3rd oximate
The overflow of device bottom is answered to the 4th oximation reaction device, continues logical ammonia, it is 4 to control reacting liquid pH value, temperature is 60-70 DEG C.Reaction solution
Cyclohexanone oxime extraction separator is flow to by the 4th oximation reaction device bottom, separator top is cyclohexanone oxime, organic solvent, decyclization
Hexanone oxime is refined, and lower floor is azanol-ammonium sulfate liquid, is recycled back to the first oximation reaction device.
The major control condition of the continuous oximate technique of two section of four Anticountra flow is：
The reaction temperature of second oximation reaction device：55-65℃
The reaction temperature of 4th oximation reaction device：60-70℃
Secondth, the pH value of the 4th oximation reaction device：4
Material ratio in first oximate device
Cyclohexanone：HAS 1.4:1 (mole)
Material ratio in 3rd oximate device
Cyclohexanone：HAS 1:4 (moles)
Always proportioning is about 1 to cyclohexanone with HAS:1~1：1.06 (moles)
Oximation reaction device is autoclave stirred reactor, autoclave stirred reactor band cooling water jecket or setting inner coil pipe, is used
Water cooling is cooled down, with controlling reaction temperature.
Oximation process two：Two section of two Anticountra flow oximate, (by taking tank reactor as an example) as shown in Figure 3.
The method two taken in the present invention is also two sections of adverse current oximate flows.A kind of this mode is using two kettles, two sections of streams
Journey, each oximate device is respectively arranged with outer circulation pump, and by forcing Matter Transfer to reach, material is uniformly mixed, and in outer circulating line peace
Fill cooler regulation reaction temperature.
The latter stage of HAS, i.e. hydrolysis latter stage are prepared, the vacuum flashing of high temperature amine aqueous solution concentration is removed water, can also
It is the solution concentration evaporation water removal of heating HAS, typically requires that HAS solution concentration is more than 0.8mol/L.
Ammonium sulfate by cyclohexanone and containing HAS is added in the first oximation reaction device, and is passed through simultaneously few
Ammonia is measured, is extracted out reaction solution by primary cycle pump, is cooled down by one-level external circulation heat exchanging device, is incited somebody to action and oximation reaction temperature dimension
Hold at 55-65 DEG C, pH value is maintained at 4 or so.Reaction solution flow to ammonium sulfate extraction separator by the first oximation reaction device bottom, plus
Organic solvent.Separator upper strata be cyclohexanone, cyclohexanone oxime liquid and organic solvent, remove cyclohexanone oxime line pump groove, after go second
Oximation reaction device；Lower floor is ammonium sulfate liquid, removes ammonium sulfate crystallization device.
Cyclohexanone, the cyclohexanone oxime liquid sent by the HAS after concentrate and by cyclohexanone oxime line pump groove are added to
Two oximate reactors, while logical ammonia, it is 4 to control reacting liquid pH value, is extracted out reaction solution by secondary cycle pump, outer by two grades
Circulation heat exchanger is cooled down, and two grades of oximation reaction temperature are maintained into 60-70 DEG C.Reaction solution is flow to by the second oximation reaction device bottom
Cyclohexanone oxime extraction separator, separator top be cyclohexanone oxime, organic solvent, go cyclohexanone oxime refine, recovery it is organic molten
Agent is recycled back to cyclohexanone oximate reaction system, and lower floor is azanol-ammonium sulfate liquid, is recycled back to the first oximation reaction device.
The major control condition of the continuous oximate technique of two section of two Anticountra flow is：
The reaction temperature of first oximation reaction device：55-65℃
The reaction temperature of second oximation reaction device：60-70℃
The pH value of first, second oximation reaction device：4
Material ratio in first oximation reaction device oximate device
Cyclohexanone：HAS 1.4:1 (mole)
Material ratio in second oximation reaction device
Cyclohexanone：HAS 1:4 (moles)
Always proportioning is about 1 to cyclohexanone with HAS:1~1：1.06 (moles)
This method flow is simple, equipment number of units is few.
Cyclohexanone oximate process key reaction condition and major influence factors are：
(1) pH value of reaction end
Cyclohexanone oximation reaction is balanced reaction, when reaching balance, and about 80% cyclohexanone is converted into cyclohexanone oxime.Merely
The molar ratio of increase reactant can not make cyclohexanone conversion complete.The water and sulfuric acid of reaction generation are reduced when taking measures
When, cyclohexanone oxime can be made to be swift in response completion.Using addition basic species in the present invention, such as ammonia, sodium carbonate etc., preferably
Ammonia, it is exactly the pH value for controlling reaction end to add alkaline matter practical function, and research is found, the pH value control of reaction end exists
Between 4~7.
(2) proportion scale
If do not used adverse current oximate flow, cyclohexanone is difficult to be totally converted.Using adverse current oximate flow, cyclohexanone and sulfuric acid
Azanol always can reach about 1 with mol ratio:1.During first paragraph oximate, cyclohexanone is excessive, can make the sulfuric acid of discharge
Hydroxylammonium sulfate is not contained in ammonium；During second segment oximate, hydroxylammonium sulfate is excessive, cyclohexanone can be made to be completely converted into hexamethylene
Ketoxime.Cyclohexanone content can reach less than 0.02% in adverse current oximate flow cyclohexanone oxime.
One-level cyclohexanone is excessive, and excessive cyclohexanone goes two grades, two grades of azanol excess, and excessive azanol goes one-level, so that hydroxyl
Amine reaches stoichiometric with cyclohexanone.
(3) oximate temperature
Oximate temperature is too high to occur a series of side reactions, and temperature is too low and cyclohexanone oxime diffusion can be made difficult, because after
End ring hexanone oxime content is big.So the common technique of adverse current oximate flow is the oximation reaction temperature difference of front-end and back-end.Before
End ring hexanone oxime content is low, and rear end cyclohexanone oxime content is high, and head temperature is low, and rear end temperature is high, therefore, conventional method needs control
The temperature of first paragraph oximation reaction processed is 55-65 DEG C, and the temperature of second segment oximation reaction is 75-80 DEG C.
But add after organic solvent, situation is just changed, second segment oximation reaction temperature can be reduced to 60-70
℃.Cyclohexanone oxime is easily dissolved in organic solvent, and this is just avoided that hot-spot and local ph are excessive, particularly can reinforcing ring
Hexanone oxime it is scattered.Cyclohexanone oxime viscosity is high, it is not easy to scattered, and cyclohexanone can be hindered to participate in reaction, and organic solvent can strengthen ring
Contact of the hexanone with hydroxylammonium sulfate, improves reaction speed.
Moreover, add after organic solvent, due to the extraction of organic solvent, easily by cyclohexanone oxime from reaction system
In separate.So as to reduce the loss of cyclohexanone and cyclohexanone oxime.
(4) stirring efficiency
Strong mixing is avoided that hot-spot and local ph are excessive, can particularly strengthen the scattered of cyclohexanone oxime.Cyclohexanone
Oxime viscosity is high, it is not easy to scattered, and cyclohexanone can be hindered to participate in reaction, and strong stirring power enhancing cyclohexanone and hydroxylammonium sulfate connect
Touch, improve reaction speed, and be conducive to controlling reaction temperature.Agitator speed is more than 500r/min under normal circumstances.
Beneficial effect：Compared with prior art, advantages of the present invention is：First, ammonia type flue gas desulfurizing is generally because in flue gas
SO2Content is low, and accessory substance HAS concentration is low, and water content is big, and cyclohexanone oximation reaction is the reaction for generating water, reduces anti-
The system water content of answering is conducive to improving reaction conversion ratio, while being more beneficial for reducing the evaporation water that Reaction Separation goes out ammonium sulfate
Amount saves energy；Secondly, the present invention improves the diffusion of reaction system, second level oximate is anti-after organic solvent is added
It is able to should carry out at a lower temperature, the conversion ratio that cyclohexanone is converted into cyclohexanone oxime is improved, in products obtained therefrom cyclohexanone oxime
Cyclohexanone generally below 0.1%, thereby reduces the consumption of cyclohexanone；Simultaneously as organic solvent extraction, the present invention
Below 0.30wt% can be reduced to by leaving cyclohexanone oxime in the inorganic phase of cyclohexanone oxime synthesis system, cyclohexanone total content, be improved
The yield of cyclohexanone oximation reaction.
Brief description of the drawings
Fig. 1 is cyclohexanone oxime process flow diagram of the present invention.
Fig. 2 is cyclohexanone oxime process flow diagram of the present invention using two section of four inverse time.
Fig. 3 is cyclohexanone oxime process flow diagram of the present invention using two section of two inverse time.
In Fig. 2,1-the first oximation reaction device；2-the second oximation reaction devices；3-the three oximate reactors；4-the four oximates are anti-
Answer device；5-ammonium sulfate extraction separator；6-cyclohexanone oxime extraction separator；7-cyclohexanone oxime line pump groove；8-azanol-ammonium sulfate
Pump groove.
In Fig. 3,1-the first oximation reaction device；2-the second oximation reaction devices；5-ammonium sulfate extraction separator；6-cyclohexanone oxime
Extraction separator；7-cyclohexanone oxime line pump groove；8-azanol-ammonium sulfate pump groove.
Embodiment：
Cyclohexanone oxime technological process of the present invention is as shown in Figure 1.Specifically, being the sulphur by cyclohexanone and containing HAS
Acid ammonium solution is added in one section of adverse current oximation reaction device, cyclohexanone in reactor：HAS mol ratio is 1.4:1, and together
When be passed through a small amount of ammonia, reaction temperature maintains 55-65 DEG C, and pH value is maintained at 4 or so.Reaction solution delivers to ammonium sulfate extraction point afterwards
From device, organic solvent toluene is added to one-level oximation reaction device or to ammonium sulfate extraction separator.Separator lower floor is inorganic phase
Ammonium sulfate, removes ammonium sulfate crystallization device；Upper strata is the organic solutions such as organic phase toluene, cyclohexanone, cyclohexanone oxime, into two
Section adverse current oximate unit.
HAS after concentrate is added in two sections of oximation reaction devices, cyclohexanone in reactor：HAS mole
Than for 1:4, while logical ammonia, it is 60-70 DEG C to control reacting liquid temperature, and pH value is 4 or so.Reaction solution is sent by two sections of oximation reaction devices
To cyclohexanone oxime extraction separator, separator upper strata is organic phase cyclohexanone oxime, organic solvent, goes cyclohexanone oxime to refine；Lower floor
For inorganic phase azanol-ammonium sulfate liquid, one section of adverse current oximate system is recycled back to.
Embodiment 1 (two section of four Anticountra flow oximate)
Such as Fig. 2,95-110 DEG C of ammonia type flue gas desulfurizing by-product of HAS solution is flashed under 82kPa (absolute pressure),
Remove part water so that hydroxylamine solution concentration is 1.76mol/L.
Ammonium sulfate by cyclohexanone and containing HAS is added to the first oximation reaction device, and fed cyclohexanone amount is
Cyclohexanone in 5.28mol/min, the first oximation reaction device：HAS mol ratio is 1.4:1, HAS amount is in solution
3.77mol/min, and a small amount of ammonia is passed through simultaneously, make solution overflow to the second oximation reaction device, continue logical ammonia, temperature maintains 60
DEG C, pH value is maintained at 4 or so.Reaction solution flow to ammonium sulfate extraction separator by the second oximation reaction device bottom, extracts to ammonium sulfate
Separator is taken to add organic solvent toluene, addition is 1004g/min, and separator upper strata is toluene, cyclohexanone, cyclohexanone oxime
Liquid, removes cyclohexanone oxime line pump groove, and lower floor is ammonium sulfate liquid, removes ammonium sulfate crystallization device.Leave the inorganic machine phase of oximate system
In, cyclohexanone+cyclohexanone oxime mass concentration is 0.27%.
Cyclohexanone, the cyclohexanone oxime liquid sent by the HAS after concentrate and by cyclohexanone oxime line pump groove are added to
Three oximate reactors, HAS inlet amount is cyclohexanone in 5.42mol/min, the 3rd oximate reactor：HAS mole
Than for 1:4, cyclohexanone amount is 1.355mol/min in solution, while logical ammonia, control reacting liquid pH value is 2 or so, and temperature is 70
℃.Reaction solution continues logical ammonia by the 3rd oximate reactor bottom overflow to the 4th oximation reaction device, and it is 4 to control reacting liquid pH value,
Temperature 70 C.Reaction solution flow to cyclohexanone oxime extraction separator by the 4th oximation reaction device bottom, and separator top is organic phase
Cyclohexanone oxime, organic solvent, go cyclohexanone oxime to refine, generation cyclohexanone oxime 5.19mol/min.Lower floor is azanol-ammonium sulfate liquid,
It is recycled back to the first oximation reaction device.
Oximation reaction device is autoclave stirred reactor, autoclave stirred reactor band cooling water jecket or setting inner coil pipe, is used
Water cooling is cooled down, with controlling reaction temperature.Always proportioning mole is 1 to cyclohexanone with HAS:1.03.
Embodiment 2 (two section of two Anticountra flow oximate)
Such as Fig. 3,95-110 DEG C of ammonia type flue gas desulfurizing by-product of HAS solution is flashed under 82kPa (absolute pressure),
Remove part water so that hydroxylamine solution concentration is 1.76mol/L.
Ammonium sulfate by cyclohexanone and containing HAS is added to the first oximation reaction device, and fed cyclohexanone amount is
Cyclohexanone in 5.28mol/min, the first oximation reaction device：HAS mol ratio is 1.4:1, HAS amount is in solution
3.77mol/min, and a small amount of ammonia is passed through simultaneously, make solution overflow to the second oximation reaction device, continue logical ammonia, pass through primary cycle
Pump extracts reaction solution out, is cooled down by one-level external circulation heat exchanging device, and temperature maintains 60 DEG C, and pH value is maintained at 4 or so.Reaction solution
Ammonium sulfate extraction separator is flow to by the first oximation reaction device bottom, organic solvent toluene is added to ammonium sulfate extraction separator,
Addition is 1004g/min, and separator upper strata is toluene, cyclohexanone, cyclohexanone oxime liquid, removes cyclohexanone oxime line pump groove, lower floor
For ammonium sulfate liquid, ammonium sulfate crystallization device is removed.Leave in the inorganic machine phase of oximate system, cyclohexanone+cyclohexanone oxime mass concentration
For 0.33%.
Cyclohexanone, the cyclohexanone oxime liquid sent by the HAS after concentrate and by cyclohexanone oxime line pump groove are added to
Two oximate reactors, HAS inlet amount is cyclohexanone in 5.12mol/min, the second oximation reaction device：HAS mole
Than for 1:4, cyclohexanone amount is 1.355mol/min in solution, while logical ammonia, control reacting liquid pH value passes through two grades 4 or so
Circulating pump extracts reaction solution out, is cooled down by second level external circulation heat exchanging device, temperature is at 70 DEG C.Reaction solution is by the second oximation reaction
Device bottom overflow to cyclohexanone oxime extraction separator, separator top is organic phase cyclohexanone oxime, organic solvent, removes cyclohexanone oxime
It is refined, generation cyclohexanone oxime 5.17mol/min.Lower floor is azanol-ammonium sulfate liquid, is recycled back to the first oximation reaction device.Cyclohexanone
Always matched with HAS mole is 1:1.03.
Comparative example 1 (two section of four Anticountra flow oximate, organic solvent-free)
By 95-110 DEG C of ammonia type flue gas desulfurizing by-product of HAS solution, flashed under 82kPa (absolute pressure), remove portion
Divide water so that HAS solution concentration is 1.76mol/L.
Ammonium sulfate by cyclohexanone and containing HAS is added to the first oximation reaction device, and fed cyclohexanone amount is
Cyclohexanone in 5.28mol/min, the first oximation reaction device：HAS mol ratio is 1.4:1, HAS amount is in solution
3.77mol/min, and a small amount of ammonia is passed through simultaneously, make solution overflow to the second oximation reaction device, continue logical ammonia, temperature maintains 60
DEG C, pH value is maintained at 4 or so.Reaction solution flow to ammonium sulfate extraction separator, separator upper strata by the second oximation reaction device bottom
For cyclohexanone, cyclohexanone oxime liquid, cyclohexanone oxime line pump groove is removed, lower floor is ammonium sulfate liquid, removes ammonium sulfate crystallization device.Leave oxime
In the inorganic machine phase of change system, cyclohexanone+cyclohexanone oxime mass concentration is 0.87%.
Cyclohexanone, the cyclohexanone oxime liquid sent by the HAS after concentrate and by cyclohexanone oxime line pump groove are added to
Three oximate reactors, azanol inlet amount is cyclohexanone in 5.42mol/min, the 3rd oximate reactor：HAS mol ratio is
1:4, cyclohexanone amount is 1.355mol/min in solution, while logical ammonia, control reacting liquid pH value is 2 or so, and temperature is at 78 DEG C.Instead
Liquid is answered by the 3rd oximate reactor bottom overflow to the 4th oximation reaction device, continues logical ammonia, it is 4, temperature to control reacting liquid pH value
78℃.Reaction solution flow to cyclohexanone oxime extraction separator by the 4th oximation reaction device bottom, and separator top is organic phase hexamethylene
Ketoxime goes cyclohexanone oxime to refine, generation cyclohexanone oxime 4.98mol/min.Lower floor is azanol-ammonium sulfate liquid, is recycled back to the first oximate
Reactor.
Oximation reaction device is autoclave stirred reactor, autoclave stirred reactor band cooling water jecket or setting inner coil pipe, is used
Water cooling is cooled down, with controlling reaction temperature.Cyclohexanone is always 1 with mol ratio with HAS:1.03.
Comparative example 2 (two section of two Anticountra flow oximate, organic solvent-free)
By 95-110 DEG C of ammonia type flue gas desulfurizing by-product of HAS solution, flashed under 82kPa (absolute pressure), remove portion
Divide water so that HAS solution concentration is 1.76mol/L.
Ammonium sulfate by cyclohexanone and containing HAS is added to the first oximation reaction device, and fed cyclohexanone amount is
Cyclohexanone in 5.28mol/min, the first oximation reaction device：HAS mol ratio is 1.4:1, azanol amount is in solution
3.77mol/min, and a small amount of ammonia is passed through simultaneously, make solution overflow to the second oximation reaction device, continue logical ammonia, pass through primary cycle
Pump extracts reaction solution out, is cooled down by one-level external circulation heat exchanging device, and temperature maintains 60 DEG C, and pH value is maintained at 4 or so.Reaction solution
Ammonium sulfate extraction separator is flow to by the first oximation reaction device bottom, separator upper strata is cyclohexanone, cyclohexanone oxime liquid, removes hexamethylene
Ketoxime line pump groove, lower floor is ammonium sulfate liquid, removes ammonium sulfate crystallization device.Leave in the inorganic machine phase of oximate system, cyclohexanone+
Cyclohexanone oxime mass concentration is 0.91%.
Cyclohexanone, the cyclohexanone oxime liquid sent by the HAS after concentrate and by cyclohexanone oxime line pump groove are added to
Two oximate reactors, azanol inlet amount is cyclohexanone in 5.12mol/min, the second oximation reaction device：HAS mol ratio is
1:4, cyclohexanone amount is 1.355mol/min in solution, while logical ammonia, control reacting liquid pH value passes through secondary cycle 4 or so
Pump extracts reaction solution out, is cooled down by second level external circulation heat exchanging device, temperature is at 78 DEG C.Reaction solution is by the second oximation reaction device bottom
Portion's overflow is to cyclohexanone oxime extraction separator, and separator top is that organic phase cyclohexanone oxime goes cyclohexanone oxime to refine, and generates hexamethylene
Ketoxime 4.96mol/min.Lower floor is azanol-ammonium sulfate liquid, is recycled back to the first oximation reaction device.Cyclohexanone is always matched somebody with somebody with HAS
Mol ratio is 1:1.03.
Analyze oximation process and organic solvent in embodiment 1,2 and comparative example 1,2 as shown in table 1 to oximate influential effect.
The oximation process of table 1 and organic solvent are to oximate influential effect
As shown in Table 1, after oximation reaction process adds organic solvent, reaction system viscosity declines, and improves system
Diffusion, leaves organic matter cyclohexanone and the reduction of cyclohexanone oxime content in the inorganic machine phase of oximate system, and cyclohexanone oximate is anti-
The yield answered is improved.In addition, two section of four kettle adverse current oximate is slightly better compared to two section of two kettle adverse current oximate effect.
Embodiment 3
Using the oximation process of embodiment 2, institute's difference is that HAS solution concentration is 0.8mol/L.
Embodiment 4
Using the oximation process of embodiment 2, institute's difference is that HAS solution concentration is 1.2mol/L.
Embodiment 5
Using the oximation process of embodiment 2, institute's difference is that HAS solution concentration is 2.4mol/L.
Embodiment 6
Using the oximation process of embodiment 2, institute's difference is that HAS solution concentration is 3.0mol/L.
Comparative example 3
Using the oximation process of embodiment 2, institute's difference is that HAS solution concentration is 0.5mol/L.
Comparative example 4
Using the oximation process of embodiment 2, institute's difference is that HAS solution concentration is 3.2mol/L.
HAS solution concentration is to the oximate influential effect such as institute of table 2 in analysis embodiment 3,4,5,6 and comparative example 3,4
Show.
Influence of the HAS solution concentration of table 2 to yield of the present invention
Note：(1) HAS solubility in water is 8.20mol/L during temperature 60 C；
(2) ammonium sulfate saturated aqueous solution concentration is 46.52wt% during temperature 60 C.
As shown in Table 2, as HAS concentration increases, oxime, ketone content slightly have reduction in inorganic phase, and ammonium sulphate content is bright
Aobvious increase；When HAS solution concentration is 0.5mol/L, ammonium sulphate content is very low in inorganic phase, the power consumption of later stage evaporative crystallization
It is larger；When HAS solubility is 3.2mol/L, crystal precipitation is arranged at extraction separator bottom, illustrates ammonium sulfate in inorganic phase
Saturation is reached, crystal, which is separated out, can cause the problems such as discharge pipe is blocked, be unfavorable for oximation reaction progress.
Claims (6)
1. a kind of method of cyclohexanone oximate, it is characterised in that：Using ammonia or ammoniacal liquor as absorbent, the titanium dioxide in flue gas is absorbed
Sulphur, prepares ammonium bisulfite, removes after solid impurity therein, is reacted with nitrite, sulfur dioxide, prepares sulphur
Sour hydroxylamine solution, concentration is improved by hydroxylammonium sulfate solution, and the method for the raising concentration is by high temperature sulphur in hydrolysis latter stage
Sour hydroxylamine solution vacuum flashing water removal, or the solution evaporation of heating hydroxylammonium sulfate are removed water, and the HAS solution concentration after water removal is
0.8~3.1mol/L, then carries out oximation reaction with cyclohexanone using the method for adverse current oximate.
During the oximation reaction, organic solvent is added, solubility of the organic solvent at 20 DEG C in water is less than
0.1%wt；
The organic solvent is at least one of benzene,toluene,xylene, methyl cyclopentane, hexamethylene.
2. the method for cyclohexanone oximate as claimed in claim 1, it is characterised in that：HAS solution after the water removal is dense
Spend for 2.4~3.0mol/L.
3. the method for cyclohexanone oximate as claimed in claim 1, it is characterised in that：In the adverse current oximation reaction, cyclohexanone
Mol ratio with HAS is 1:1~1:1.06.
4. the method for cyclohexanone oximate as claimed in claim 1, it is characterised in that：The adverse current oximate is two sections of adverse current oximates
Or multistage counter current oximate.
5. the method for cyclohexanone oximate as claimed in claim 4, it is characterised in that：Two sections of described adverse current oximates, wherein the
One section of material cyclohexanone：HAS is 1.4:1, second segment material cyclohexanone：HAS ratio is 1:4.
6. the method for cyclohexanone oximate as claimed in claim 4, it is characterised in that：Two sections of adverse current oximates, every section by one
Individual or two reactor compositions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510698820.7A CN105384656B (en) | 2015-10-23 | 2015-10-23 | A kind of method of cyclohexanone oximate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510698820.7A CN105384656B (en) | 2015-10-23 | 2015-10-23 | A kind of method of cyclohexanone oximate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105384656A CN105384656A (en) | 2016-03-09 |
| CN105384656B true CN105384656B (en) | 2017-08-25 |
Family
ID=55417483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510698820.7A Active CN105384656B (en) | 2015-10-23 | 2015-10-23 | A kind of method of cyclohexanone oximate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105384656B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107089924B (en) * | 2016-09-23 | 2019-03-05 | 河北美邦工程科技股份有限公司 | A kind of azanol, hydroxylamine salt, cyclohexanone oxime combined producing process |
| CN108409590B (en) * | 2018-04-02 | 2020-11-10 | 河北工业大学 | Betaine hydrochloride hydroxylamine, and preparation method and application thereof |
| CN110498748B (en) * | 2019-09-17 | 2022-07-12 | 万华化学集团股份有限公司 | Application of L-arginine and derivatives thereof in preparing cyclododecanone oxime and method for preparing cyclododecanone oxime |
| CN113877493B (en) * | 2021-08-24 | 2023-06-27 | 浙江中巨海锐科技有限公司 | Continuous preparation system and method for cyclododecanone solution oxime |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL6513426A (en) * | 1965-10-16 | 1967-04-17 | ||
| CN101058550A (en) * | 2007-04-11 | 2007-10-24 | 巨化集团公司锦纶厂 | Preparation method for diacetylmonoxime |
| CN103483221A (en) * | 2012-06-12 | 2014-01-01 | 刘建青 | Preparation method of cyclohexanone oxime |
| CN102755823B (en) * | 2012-08-10 | 2014-02-12 | 江山市泰格化工有限公司 | Method for desulfurizing high-sulphur boiler flue gas to prepare high-purity ammonium bisulfite |
| CN103159191B (en) * | 2013-03-25 | 2016-04-06 | 浙江圣安化工有限公司 | A kind of preparation method of hydroxylammonium salt |
-
2015
- 2015-10-23 CN CN201510698820.7A patent/CN105384656B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105384656A (en) | 2016-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105384656B (en) | A kind of method of cyclohexanone oximate | |
| CN103159191B (en) | A kind of preparation method of hydroxylammonium salt | |
| CN102531056A (en) | Method for cleaner production of sodium vanadate and sodium chromate by pressure leaching of vanadium slag | |
| CN102923664B (en) | Method for producing hydrogen fluoride by virtue of gas-solid-liquid associative reaction method | |
| CN103030207B (en) | Method for treating ammonia desulfurization waste liquid by oxidation method | |
| CN105417509B (en) | The separation method of sulfuric acid and phosphoric acid in a kind of preparation of nitrosylsulfuric acid and industrial waste acid | |
| CN105348145B (en) | The method of ammonia type flue gas desulfurizing by-product cyclohexanone oxime | |
| CN109748805A (en) | The method of liquid ammonia process for caustic soda purification production isopropanolamine | |
| CN104387322A (en) | Preparation method for caprolactam with low byproducts of ammonium sulfate | |
| CN210215203U (en) | Ammonolysis reaction system | |
| CN102828037A (en) | Method of preparing low-silicon low-phosphorus potassium metavanadate solution from vanadium slag | |
| CN104829494A (en) | Energy-saving urea production system and production process thereof | |
| CN104086362A (en) | Method for recycling organic solvents of wastewater generated in synthesis of hydrazine hydrate by ketazine method | |
| CN101333197B (en) | Method for producing melamine and co-producing ammine and ammonium hydrogen carbonate | |
| CN104910031A (en) | Method for co-producing glycine and hydantoin, and apparatus thereof | |
| CN113877493B (en) | Continuous preparation system and method for cyclododecanone solution oxime | |
| CN102659650B (en) | Device and method for preparing DL-methionine salt | |
| CN102502566A (en) | Technology for synthesizing lithium hexafluorophosphate | |
| CN108706610A (en) | A method of ammonia and high-quality gypsum are recycled by ammonium sulfate | |
| CN104557721A (en) | Method for producing 5,5-dimethylhydantoin | |
| CN105314610A (en) | Preparation method for hydroxylammonium chloride | |
| CN216946815U (en) | Device for separating caprolactam from caprolactam sulfate and co-producing compound fertilizer | |
| CN111548274A (en) | Method for preparing methyl nitrite by utilizing reaction composite reinforcement | |
| CN112010783B (en) | Ammonolysis reaction system, taurine intermediate sodium taurate and preparation method of taurine | |
| CN210506159U (en) | Reaction device for continuously preparing 6-aminocapronitrile |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder |
Address after: No. 3 horses horses Science Park Avenue in Qixia District of Nanjing City, Jiangsu province 210049 Patentee after: SINOPEC NANJING ENGINEERING & CONSTRUCTION Inc. Patentee after: Sinopec Engineering (Group) Co.,Ltd. Address before: 211112 No. 1189, Jian Jian Road, Jiangning District, Jiangsu, Nanjing Patentee before: SINOPEC NANJING ENGINEERING & CONSTRUCTION Inc. Patentee before: Sinopec Engineering (Group) Co.,Ltd. |
|
| CP02 | Change in the address of a patent holder |